Method of preparing chiral dichloro chrysanthemic acid using immobilized ester

A technology of permethrin and permethrin, applied in the direction of fermentation, etc., can solve the problems of limited production and use, difficulty in obtaining bacterial species, low activity, etc., and achieves good stability, reduced share, and good stability. Effect

Inactive Publication Date: 2003-07-02
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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Problems solved by technology

[0009] In the above-mentioned literature, the pig liver esterase resolution method uses enzymes with high activity to obtain R(+)-trans-permethrin with an optical purity of 90%. However, the price of pig liver esterase is relatively high. There are certain limitations in use, which need to be solved by enzyme immobilization
[0010] Arthrobacter globosa esterase resolution method, when the hydrolysis rate is 18.0%, the optical purity of R(+)-trans-permethrin can reach = 88.9%. However, this strain is difficult to obtain, and without mutagenesis or Genetically engineered strains have relatively low viability
[0011] There is no literature report on the preparation of chiral R(+)-trans-permethrin by immobilized esterase kinetic resolution method

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Embodiment 1: Take 0.1M NaH 2 PO 4 -Na 2 HPO 4 Buffer solution (pH = 8.0) 10ml, placed in a Erlenmeyer flask, add racemic permethrin methyl ester (purity 98.50%, the ratio of four isomers: S(-)-cis=25.34%, R (+)-cis=25.34%, S(-)-trans=23.94%, R(+)-trans=23.94%) 1.0g (4.46mmol), non-ionic surfactant Tween 80, 50mg, shake evenly, Add immobilized porcine liver esterase (by self-made free porcine liver esterase (10000U / g), immobilize on the natural amino polysaccharide of glutaraldehyde activation with the covalent binding method and obtain, and activity recovery is 90.0%, wet immobilization The unit activity of the enzyme is 29.2U / g) 50U (international units). After shaking (200 rpm) at 40°C for 24 hours, the immobilized esterase is separated from the reaction solution by centrifugation or filtration.

[0031] After the reaction solution was acidified with concentrated hydrochloric acid, it was extracted with 4-methyl-2-pentanone (10ml, twice), and then an equal volume...

Embodiment 2

[0033] Embodiment 2: get immobilized pig liver esterase (by self-made free pig liver esterase 10000U / g, covalently bonded and immobilized on the natural amino polysaccharide activated by glutaraldehyde, the activity recovery is 40.0%, wet immobilized The unit activity of enzyme is 10.4U / g), carry out hydrolysis reaction and analysis and determination by the same method and condition of embodiment 1, obtain chiral permethrin 93mg, productive rate is 9.98%, is 41.74% of theoretical productive rate. The composition ratio of the four isomers was determined as follows: S(-)-cis=0.02%, R(+)-cis=0.02%, S(-)-trans=9.77%, R(+)-trans=90.19 %.

Embodiment 3

[0034] Embodiment 3: The immobilized pig liver esterase recovered and preserved in Example 1 was hydrolyzed and analyzed under the same method and conditions as in Example 1, and the immobilized esterase was separated and recovered and recycled for more than 10 times, the 11th time After the reaction, 89 mg of chiral permethrin was obtained with a yield of 9.55%, which was 39.95% of the theoretical yield. The composition ratio of its four isomers is: S(-)-cis=0.17%, R(+)-cis=0.27, S(-)-trans=13.47%, R(+)-trans=86.11%.

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Abstract

A process for preparing chiral dichlorochrysanthemic acid from fixed esterase includes such steps as covalence-binding esterase to activated dual-functional group carrier, adding the recemic dichlorochrysanthemate, non-ionic surfactant and fixed esterase in a buffering solution, catalytic hydrolysis, separating the fixed esterase from reaction liquid, flushing the fixed esterase with buffering liquid, acidifying the reaction liquid, extracting in organic solvent, saponifying the organic phase to make dichlorochrysanthemic acid in water phase, acidifying and crystallizing. Its advantages are high speed, and high selectivity.

Description

technical field [0001] The invention relates to a method for preparing permethrin, in particular to a method for preparing chiral R(+)-trans-permethrin with immobilized esterase. Background technique [0002] Permethrinic acid (also known as DV chrysanthemic acid, English name Permethrinic acid) is an important intermediate compound composed of acid moieties in the synthesis of pyrethroid pesticides. Permethrin, i.e. 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid, has the following structure: [0003] Because there are two chiral carbon atoms on its cyclopropane ring, it has two configurations of R (+) and S (-), as well as two isomers of cis and trans, and there are four isomers in total. As the acid moiety of pyrethroid pesticides, different isomers of permethrin have significant differences in their insecticidal efficacy. Among them, chiral R(+) chrysanthemic acid is an effective body, while chiral S(-) chrysanthemic acid is an invalid body; for cis and...

Claims

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Application Information

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IPC IPC(8): C12P7/40
Inventor 邵昌平刘韧白长敏潘桂枝韩梅郑卓
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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